CN104592004B - A kind of method of refining long-chain organic acid - Google Patents
A kind of method of refining long-chain organic acid Download PDFInfo
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Abstract
The invention discloses the process for purification of a kind of fermentation organic acid.The method includes: I, general terminate fermentation liquid heat inactivation；II, acidifying make organic acid crystallization separate out, it is thus achieved that organic acid crystallization liquid；III, organic acid crystallization liquid or the aqueous organic acid filter cake that is filtrated to get are mixed with ether organic solvent make organic acid dissolve, wherein add appropriate trinitrophenol, then carry out organic facies and aqueous phase separation；IV, separate after organic facies scrubbed after, add adsorbent, filtering and removing solid content；The organic facies that V, step IV obtain is cooled to organic acid crystallization and separates out, and through filtering, is dried to obtain refined organic acid production.The inventive method uses ether organic solvent and trinitrobenzene phenol treating organic acid, not only shortens technological process, saves equipment, time and energy consumption etc. and puts into, and can obtain the polymer grade product that purity is high, total nitrogen content is low, is more suitable for industrialized production.
Description
Technical field
A kind of method that the present invention relates to refining long-chain organic acid, particularly obtains high purity long chain organic from fermentation liquid
The method of acid.
Background technology
Long chain organic acid formula is generally CnH2n-2O4, wherein n is 10-18, is that microorganism utilizes the fermentations such as liquid wax to obtain
Metabolite.Its fermentation liquid is complicated heterogeneous system, wherein contains unreacted carbon source, microbial cell and fragment, not
The culture medium utilized and metabolite and the secretions etc. of microorganism, wherein contain a large amount of protein, pigment and ash
Grade impurity, has a strong impact on purity and the application of product, and brings difficulty with refined to the extraction of this kind organic acid.
At present, the highest to this kind organic acid purity requirement on market, the particularly purity requirement of polymer grade is higher, typically
Require that organic acid mono-acid purity, at more than 98.5wt%, total nitrogen ＜ 30 g/g, the most only purifies could obtain with organic solvent method
Meet this polymer grade product required, and generally, even if purity reaches requirement, its total nitrogen content is still relatively inaccessible to want
Ask.
In long-chain biatomic acid process for purification disclosed in CN01142806.6, with long-chain biatomic acid dry powder as raw material, use alcohol
Class makees solvent refining long-chain biatomic acid.Binary acid in this method first fermentation liquid is first after activated carbon adsorption, then acidizing crystal, mistake
Filter, wash and be dried binary acid crystalli-zation cake and obtain long-chain biatomic acid dry powder, then use organic solvent to refine.The method
In, the solvent that refined binary acid uses is alcohols, when heating for dissolving, alcohol easily with binary acid generation esterification, cause finally
The reduction of product purity, limits the application in terms of polymerization.The raw material that the method refines is that aqueous filter cake obtains after drying
To binary acid dry powder, raw aqueous quantitative limitation is reduced the operating flexibility of the method, add the equipment that thick acid is dried, lead
Cause this technological process longer, add production cost.When organic solvent refines binary acid, use adsorbent typically can reach de-
The requirement of color, but still more difficult removing small molecular protein therein, make total nitrogen content undesirable.
In long-chain biatomic acid process for purification disclosed in CN200410018255.7, first fermentation method reactant liquor is carried out pre-place
Reason, to remove thalline therein and residual alkane or fatty acid, obtains organic acid clear liquid, then carries out acidizing crystal, acidifying knot
Brilliant liquid obtains organic acid crude product through filter press again；Finally the crude product obtained is passed through wiped film vaporization, short course distillation device at height
Refine under vacuum condition or use organic solvent to refine.After the binary acid crude product that the method obtains and solvent mixed dissolution, do not have
Taking the removings such as filtration to go the operating procedure of insoluble impurities, so during decrease temperature crystalline, insoluble impurities necessarily adsorbs knot
Brilliant surface, have impact on product purity, brings bad impact to the application of product.And the solvent refining binary in the method
Acid process, includes the solvent recrystallization operation of twice, and solvent consumption is relatively big, adds the burden that solvent recovery is refined, leads
Cause operating process is complex, and the highest only 98.75wt% of binary acid mono-acid purity using solvent method to be refining to obtain,
When production is slightly fluctuated, it is possible to can not get qualified product.
Summary of the invention
For the deficiencies in the prior art, a kind of method that the invention provides refining long-chain organic acid.With prior art phase
Ratio, the inventive method technique is simple, and energy consumption is low, and supplies consumption is few, and obtained organic acid purity is high, and nitrogen content and pigment etc. are miscellaneous
Matter content is low, is suitable for industrialized production.
The method of the present invention a kind of refining long-chain organic acid, including:
I, general terminate fermentation liquid heat inactivation；
II, acidifying make organic acid crystallization separate out, it is thus achieved that organic acid crystallization liquid；
III, organic acid crystallization liquid or the organic acid filter cake that is filtrated to get are mixed with organic solvent make organic acid dissolve, institute
The organic solvent stated be carbon number be the ethers of 2 ~ 8, in above-mentioned system add trinitrophenol, addition is organic acid dry basis
1 ~ 15 wt%, the preferably 2 ~ 5wt% of amount (the theoretical acid content of fermentation liquid), carries out organic facies and aqueous phase separation after mix homogeneously；
After organic phase washed with water after IV, separation, add adsorbent, filtering and removing solid content；
The organic facies that V, step IV obtain is cooled to organic acid crystallization and separates out, and through filtering, is dried to obtain refined organic acid
Product.
In the inventive method, terminating fermentation liquid described in step I is the metabolite that microorganism utilizes that the fermentation of liquid wax obtains,
The organic acid molecule formula wherein contained is CnH2n-2O4, wherein n is 10-18, and organic acid can be single a kind of organic acid, also
It can be mixed organic acid.After terminating fermentation liquid heat inactivation, can carry out the impurity such as filtering and removing thalline, filtration can use
The conventional methods such as membrane filtration and equipment.Can also in step III the impurity such as separation removal thalline.Heat inactivation temperature is generally
75 DEG C～100 DEG C.
In the inventive method, the acidifying described in step II can use conventional method to carry out.The pH value of described acidifying is 2.0
~ 4.0, heating-up temperature is 80 ~ 100 DEG C.The acid used by acidifying that the present invention is above-mentioned can be the H of any concentration2SO4、HNO3、HCl
Or H3PO4。
Organic solvent used by step III is ethers, and the carbon number of described ethers is 2 ~ 8, preferably ether, propyl ether, different
One or more of propyl ether, butyl ether, diisobutyl ether, amyl ether, isoamyl oxide, hexyl ether etc., more preferably positive propyl ether, diisopropyl ether, just
One or more of butyl ether, diisobutyl ether, isoamyl oxide etc..
In the inventive method, organic solvent is 1:1 ~ 15:1, preferably 2:1 ~ 7:1 with the weight ratio of organic acid butt.Have
Machine acid crystal liquid or organic acid filter cake dissolve the most in a heated condition with organic solvent, and heating-up temperature is generally 80 DEG C ~ 150
DEG C, preferably 90 ~ 120 DEG C, determine with specific reference to the boiling point selecting solvent, generally below the boiling temperature of used solvent.
In the inventive method, step IV can add deionized water wash organic facies once or more, and separate
Go out aqueous phase.
In the inventive method, the adsorbent in step IV is one or more in activated carbon, active hargil etc., is preferably
Activated carbon, addition is the 0.01wt% ~ 2.0wt% of organic acid butt weight, preferably 0.01wt% ~ 1.0wt%, and adsorption time is
30min ~60min。
In the inventive method, till in step V, crystallisation by cooling temperature generally makes organic acid sufficient crystallising, temperature is generally
10 DEG C～30 DEG C.
In the inventive method, the organic solvent filtrate obtained in step V, can recycle.
The inventive method can obtain the organic acid production of highly purified single kind, it is also possible to obtain mixed organic acid produces
Product.
Although it is this area conventional method that organic solvent method refines this kind organic acid, but in existing method use the suitableeest
Preferably solvent and optimal process route, also can only obtain purity and is slightly above the purity of product quality indicator requirement (98.5%), and this is right
The steady production of commercial plant is disadvantageous, when production is slightly fluctuated, it is possible to can not get qualified product.The inventive method
The ether solvent used and the synergism of trinitrophenol can make little molecule organic nitrogen and the pigment etc. dissolved in solvent phase
Efficiently it is transferred in aqueous phase, and more than 99.5% and total nitrogen is little only to use minimal amount of adsorbent to can be obtained by mono-acid purity
Organic acid production in 30 g/g.In the art, it has been very difficult that purpose product quality reaches polymer grade index request,
Purity often improves 0.1 percentage point and total nitrogen 1 g/g of reduction on this basis is all the most difficult, and is the most all to have weight
Wanting meaning and value, this, to ensureing commercial plant steady running, improves the aspects such as conforming product rate, has important effect,
Quality impact on polymerization products such as follow-up synthesizing engineering plastics is also obviously.
The inventive method, while obtaining high-purity organic acid production, also has technical process simple, and energy consumption is low, thing
Material consumes the advantages such as few.
Detailed description of the invention
The process for purification of the present invention is further illustrated below by embodiment.In the present invention, wt% is mass fraction.
In the inventive method, containing liquid wax, thalline, the culture medium not utilized, metabolite and microorganism in fermentation liquid
Secretions etc., wherein contain the impurity such as a large amount of protein, pigment.Organic acid crystallization liquid can use this area common
Method obtains, as used at least one scheme following:
(1) being heated by termination fermentation liquid and stand, dividing the liquid wax going to upper strata, then cooling filtration sterilization, obtain filtrate
It is acidified with acid to pH 2.0 ~ 4.0, and heats simultaneously, obtain organic acid crystallization liquid, or organic acid solution is filtrated to get filter cake；
Actual conditions is: will terminate fermentation liquid and heat 75 DEG C ~ 100 DEG C, and stand, then divide the liquid wax that upper strata remains, then
It is cooled to 60 DEG C ~ 90 DEG C, through microfiltration and/or ultrafiltration apparatus, is filtered to remove the impurity such as thalline and obtains clear liquid, the clear liquid obtained
Add acid for adjusting pH value to 2.0 ~ 4.0, and be heated to 80 DEG C ~ 100 DEG C, obtain organic acid crystallization liquid, or organic acid solution is filtered
To filter cake.
(2) termination fermentation liquid is heated to 75 DEG C ~ 100 DEG C, and is acidified to pH value 2.0 ~ 4.0, stand, separate and recover liquid
Wax, obtains organic acid crystallization liquid；
(3) fermentation liquid is heated to 75 DEG C ~ 90 DEG C, enters microfiltration or ultrafiltration apparatus, removing thalline and liquid wax, the filter obtained
Liquid is acidified to pH value 2.0 ~ 4.0, and is heated to 80 DEG C ~ 100 DEG C, obtains organic acid crystallization liquid.
Embodiment 1
Take the C that 200ml is obtained by Candida tropicalis fermentation12H22O4Fermentation liquid, concentration is 160g/l.It is heated to 80
DEG C, stand 2h, divide the liquid wax going solution to remain, be filtered to remove thalline, obtain C12H22O4Fermentation clear liquid, uses H2SO4PH value is adjusted
To 3.0 and heat, obtain organic acid crystallization liquid.
The C obtained12H22O4Organic acid crystallization liquid and positive propyl ether (positive propyl ether and C12H22O4Weight ratio is 7:1) heat and mix
Close, be all dissolved in solvent phase (solution temperature 80 DEG C) to organic acid crystal, in mixed liquor, add 0.65 g trinitrophenol,
Heated and stirred 20min, static 60min, point sub-cloud aqueous phase is continued under solution temperature；30ml deionization is added again in solvent phase
Water washing organic facies, divides aqueous phase again；With backward organic facies adds 0.3g activated carbon insulation decolouring 30min, then filter
Removing activated carbon, the organic facies after decolouring is cooled to 30 DEG C of crystallizations and obtains C12H22O4Organic acid, drying step obtains
Product.Product quality is shown in Table 1.
Embodiment 2
Take 200ml and obtained C by Candida tropicalis fermentation12H22O4Organic acid fermentation liquid, concentration is 164g/l.It is heated to
85 DEG C, use H2SO4PH value is adjusted to 3.5, stands 2h, divide the liquid wax going solution to remain, obtain the C of mycetome12H22O4Organic acid
Crystal solution.
The C obtaining mycetome12H22O4Organic acid crystallization liquid and n-butyl ether (n-butyl ether and C12H22O4Weight ratio is 6:1)
It is mixed and heated to 90 DEG C, in mixed liquor, adds 1.5g trinitrophenol, static after continuing heated and stirred 30min at 90 DEG C
30min, point sub-cloud aqueous phase (the salt complex precipitate etc. that the thalline wherein settled and reaction generate removes with point water)；Again
In solvent phase, add 50ml deionized water wash organic facies, again divide aqueous phase；In organic facies, add 0.2g activated carbon protect
Temperature decolouring 30min, is then filtered to remove activated carbon, and the organic facies after decolouring is cooled to 20 DEG C of crystallizations and obtains C12H22O4Organic
Acid, then obtain product through filtration drying step.Product quality is shown in Table 1.
Embodiment 3
Take 200ml and obtained C by Candida tropicalis fermentation13H24O4Organic acid fermentation liquid, concentration is 154g/l.It is heated to
80 DEG C, through ceramic micro filter membrane filtration, the liquid wax of removing thalline and remnants obtains filtrate.H is added in filtrate2SO4Regulation pH value is extremely
2.4, and it is heated to 95 DEG C, obtain C13H24O4Organic acid crystallization liquid, is cooled to room temperature and is filtrated to get organic acid filter cake.
The C obtained13H24O4Organic acid filter cake and n-butyl ether (n-butyl ether and C13H22O4Weight ratio is 3:1) mixing, to mixed
Close and liquid adds 0.95g trinitrophenol, after continuing to add hot mixing 40min at 98 DEG C, static 60min, point sub-cloud aqueous phase；
In solvent phase, add 60ml deionized water wash organic facies again, again divide aqueous phase；Add 0.15g activated carbon to organic facies to protect
Temperature decolouring 30min, is then filtered to remove activated carbon, and the organic facies after decolouring is cooled to 18 DEG C of crystallizations and obtains C13H24O4Organic
Acid, then obtain product through filtration drying step.Product quality is shown in Table 1.
Embodiment 4
Take the C that 200ml concentration is 145g/l14H26O4Organic acid fermentation liquid, is heated to 85 DEG C, through ceramic micro filter membrane filtration,
The liquid wax of removing thalline and remnants obtains filtrate.H is added in filtrate2SO4Regulation pH value is to 4.0, and is heated to 95 DEG C, obtains
C14H26O4Organic acid crystallization liquid.
The C obtained14H26O4Organic acid crystallization liquid and diisopropyl ether (diisopropyl ether and C14H22O4Weight ratio is 6:1) mixing, to
Mixed liquor adds 1.15 g trinitrophenols, after continuing to add hot mixing 60min at 65 DEG C, static 20min, point sub-cloud
Aqueous phase；In solvent phase, add 30ml deionized water wash organic facies again, again divide aqueous phase；0.20g is added in organic facies
Activated carbon insulation decolouring 30min, is then filtered to remove activated carbon, and the organic facies after decolouring is cooled to 25 DEG C of crystallizations and obtains
C14H26O4Organic acid, then obtain product through filtration drying step.Product quality is shown in Table 1.
Comparative example 1
Take the C that 200ml concentration is 151g/l14H26O4Organic acid fermentation liquid, is heated to 85 DEG C, through ceramic micro filter membrane filtration,
The liquid wax of removing thalline and remnants obtains filtrate.H is added in filtrate2SO4Regulation pH value is to 4.0, and is heated to 95 DEG C, obtains
C14H26O4Organic acid crystallization liquid.
The C obtained14H26O4Organic acid crystallization liquid and ethanol (ethanol and C14H22O4Weight ratio is 6:1) mixing, to mixing
Liquid adds 1.10 g trinitrophenols, after continuing to add hot mixing 60min at 68 DEG C, static 20min, point sub-cloud aqueous phase；
In solvent phase, add 30ml deionized water wash organic facies again, again divide aqueous phase；0.20g activated carbon is added in organic facies
Insulation decolouring 30min, is then filtered to remove activated carbon, and the organic facies after decolouring is cooled to 25 DEG C of crystallizations and obtains C14H26O4Organic
Acid, then obtain product through filtration drying step.Product quality is shown in Table 1.
Comparative example 2
Take the C that 200ml concentration is 155g/l14H26O4Organic acid fermentation liquid, is heated to 85 DEG C, through ceramic micro filter membrane filtration,
The liquid wax of removing thalline and remnants obtains filtrate.H is added in filtrate2SO4Regulation pH value is to 4.0, and is heated to 95 DEG C, obtains
C14H26O4Organic acid crystallization liquid.
The C obtained14H26O4Organic acid crystallization liquid and acetone (acetone and C14H22O4Weight ratio is 6:1) mixing, to mixing
Liquid adds 1.15 g trinitrophenols, after continuing to add hot mixing 60min at 50 DEG C, static 20min, point sub-cloud aqueous phase；
In solvent phase, add 30ml deionized water wash organic facies again, again divide aqueous phase；0.20g activated carbon is added in organic facies
Insulation decolouring 30min, is then filtered to remove activated carbon, and the organic facies after decolouring is cooled to 25 DEG C of crystallizations and obtains C14H26O4Organic
Acid, then obtain product through filtration drying step.Product quality is shown in Table 1.
Comparative example 3
Take the C that 200ml concentration is 145g/l14H26O4Organic acid fermentation liquid, is heated to 85 DEG C, through ceramic micro filter membrane filtration,
The liquid wax of removing thalline and remnants obtains filtrate.H is added in filtrate2SO4Regulation pH value is to 4.0, and is heated to 95 DEG C, obtains
C14H26O4Organic acid crystallization liquid.
The C obtained14H26O4Organic acid crystallization liquid and diisopropyl ether (diisopropyl ether and C14H22O4Weight ratio is 6:1) mixing,
After continuing to add hot mixing 60min at 65 DEG C, static 20min, point sub-cloud aqueous phase；30ml deionized water is added again in solvent phase
Washing organic facies, divides aqueous phase again；In organic facies, add 0.20g activated carbon insulation decolouring 30min, be then filtered to remove work
Property charcoal, the organic facies after decolouring is cooled to 25 DEG C of crystallizations and obtains C14H26O4Organic acid, then obtain product through filtration drying step.
Product quality is shown in Table 1.
Table 1 organic acid production quality
Claims (13)
1. a process for purification for fermentation organic acid, including:
I, general terminate fermentation liquid heat inactivation；
II, acidifying make organic acid crystallization separate out, it is thus achieved that organic acid crystallization liquid；
III, organic acid crystallization liquid or the organic acid filter cake that is filtrated to get are mixed with organic solvent make organic acid dissolve, described
Organic solvent be carbon number be the ethers of 2 ~ 8, in above-mentioned system add trinitrophenol, addition is organic acid butt weight
1 ~ 15 wt%, carries out organic facies and aqueous phase separation after mix homogeneously；
After organic phase washed with water after IV, separation, add adsorbent, filtering and removing solid content；
The organic facies that V, step IV obtain is cooled to organic acid crystallization and separates out, and through filtering, is dried to obtain refined organic acid production.
The most in accordance with the method for claim 1, it is characterised in that described ethers is ether, propyl ether, diisopropyl ether, butyl ether, different
Butyl ether, amyl ether, isoamyl oxide, hexyl ether one or more.
The most in accordance with the method for claim 1, it is characterised in that described ethers is positive propyl ether, diisopropyl ether, n-butyl ether, isobutyl
Ether, isoamyl oxide one or more.
The most in accordance with the method for claim 1, it is characterised in that described organic acid molecule formula is CnH2n-2O4, wherein n is
10-18, organic acid is single a kind of organic acid or is mixed organic acid.
The most in accordance with the method for claim 1, it is characterised in that step I heat inactivation temperature is 75 DEG C～100 DEG C.
The most in accordance with the method for claim 1, it is characterised in that described in step II, the pH value of acidifying is 2.0 ~ 4.0, heating temperature
Degree is 80 DEG C ~ 100 DEG C, and the acid used by acidifying is the H of any concentration2SO4、HNO3, HCl or H3PO4。
The most in accordance with the method for claim 1, it is characterised in that in step III, organic solvent and the weight of organic acid butt
Ratio is 1:1 ~ 15:1.
The most in accordance with the method for claim 1, it is characterised in that in step III, organic solvent and the weight of organic acid butt
Ratio is 2:1 ~ 7:1.
The most in accordance with the method for claim 1, it is characterised in that in step III, organic acid crystallization liquid or organic acid filter cake with
Organic solvent dissolves in a heated condition, and heating-up temperature is 80 DEG C ~ 150 DEG C.
The most in accordance with the method for claim 1, it is characterised in that the adsorbent in step IV is in activated carbon, active hargil
One or more, addition is the 0.01wt% ~ 2.0wt% of organic acid butt weight, and adsorption time is 30min ~ 60min.
11. in accordance with the method for claim 1, it is characterised in that the adsorbent addition in step IV is organic acid dry basis
0.01wt% ~ the 1.0wt% of amount.
12. in accordance with the method for claim 1, it is characterised in that in step II, and organic acid crystallization liquid uses following at least one
The scheme of kind:
(1) termination fermentation liquid it is heated to 75 DEG C ~ 100 DEG C and stands, dividing the liquid wax going to upper strata, then cooling filtration sterilization,
Obtain filtrate to be acidified with acid to pH2.0 ~ 4.0, and be simultaneously heated to 80 DEG C ~ 100 DEG C, obtain organic acid crystallization liquid；
(2) termination fermentation liquid is heated to 75 DEG C ~ 100 DEG C, and is acidified to pH value 2.0 ~ 4.0, stand, separate and recover liquid wax,
To organic acid crystallization liquid；
(3) fermentation liquid is heated to 75 DEG C ~ 90 DEG C, enters microfiltration or ultrafiltration apparatus, removing thalline and liquid wax, the filtrate obtained acid
Change to pH value 2.0 ~ 4.0, and be heated to 80 DEG C ~ 100 DEG C, obtain organic acid crystallization liquid.
13. in accordance with the method for claim 1, it is characterised in that in step V, crystallisation by cooling temperature is for making organic acid fully tie
Till crystalline substance, temperature is 10 DEG C～30 DEG C.
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| CN112794799B (en) * | 2019-10-28 | 2022-08-12 | 中国石油化工股份有限公司 | Method for reducing solvent evaporation amount in binary acid refining process |
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Effective date of registration: 20230814 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |